Age resistant resin compositions and admixtures useful as adhesives

ABSTRACT

Age resistant resin which comprises a composition selected from (A) a composition having a softening point in the range of 0° C to about 140° C comprising units derived from selected aliphatic diolefins and aliphatic monoolefins, which can be modified with units derived from dicyclopentadiene, and certain vinyl aromatic compounds, and selected phenol or amine type compounds and (B) a composition having a softening point in the range of about 60° C to about 110° C comprising units derived from monoolefins and vinyl aromatic compounds, which can be modified with aliphatic diolefins, and selected phenol and amine type compounds. Such age resistant resins have particular utility when admixed with various rubbery materials and thermoplastics to create pressure sensitive adhesives and hot melt adhesives.

This invention relates to age resistant polymerization compositions anda method for preparing age resistant materials. The inventionparticularly relates to tackifying resins having improved oxidative ageresistance, and compositions comprising an admixture of such resins andmaterials such as thermoplastics and rubber compositions.

Many resins and practically all types of rubber, both natural andsynthetic, are known to be susceptible to deterioration resulting fromprolonged exposure to oxidative aging. Various age resistors have beenmixed with various resins and rubbers to inhibit such a deterioration,however, many times such stabilizers have tended to migrate orvolatilize especially when such resins or compositions containing suchresins ae exposed to conditions involving elevated temperatures overprolonged periods of time under atmospheric conditions.

It is therefore an object of this invention to provide resins, andvarious admixtures thereof with other materials, which are resistant tooxidative aging and to provide a method for preparing such resins.

In accordance with this invention, an age resistant resin comprises acomposition selected from (A) a composition having a softening point inthe range of 0° C to about 140° C, preferably about 20° C to about 110°C and especially about 80° C to about 110° C, comprising (1) about 40 toabout 80 weight percent units derived from aliphatic diolefins having 4to 8, preferably 4 to 6, carbon atoms, where one of the double bonds isalpha to a terminal carbon atom, (2) about 60 to about 20 weight percentunits derived from aliphatic monoolefins having 3 to 8, preferably 4 to6, carbon atoms, where the double bond is alpha or beta to a terminalcarbon atom, where the mole ratio of diolefin to monoolefin is about0.7:1 to about 2:1, (3) about 0 to about 40 weight percent units derivedfrom at least one of dicyclopentadiene and a vinyl aromatic compoundselected from styrene and α-methyl styrene and (4) about 0.2 to about 2weight percent units derived from at least one selected phenol or aminetype compound and (B) a composition having a softening point in therange of about 60° C to about 110° C comprising (1) about 0 to about 40weight percent units derived from said diolefins, (2) about 10 to about40 weight percent units derived from said monoolefins, (3) about 40 toabout 70 weight percent units derived from a vinyl aromatic compoundselected from styrene and alpha methyl styrene and (4) about 0.2 toabout 2 weight percent units derived from at least one of said selectedphenol or amine compounds, where said phenol and amine compounds areselected from (i) a phenolic compound having the structural formula##STR1## where R₁ and R₂ are radicals selected from t-butyl, t-hexyl,α-phenethyl, methyl, isopropyl and hydrogen radicals, where X and Y areindividually selected from the groups consisting of ##STR2## and --CNand where X is further selected from hydrogen, wherein R₃, R₄, R₅ and R₆are radicals selected from the group consisting of hydrogen andsaturated alkyl radicals having 1 to 4 carbon atoms (ii) a phenolicmaterial having the structural formula ##STR3## where R₁ and R₂ are ashereinbefore identified, where X₁ is selected from the groups consistingof --0--, --CH₂ O, --NH, --CH₂ NH, and --CH₂ OCH₂ --CH₂ --O and where Y₁is selected from the groups consisting of ##STR4## where R₈ is selectedfrom hydrogen and methyl radicals and where R₉ and R₁₀ are individuallyselected from hydrogen, methyl and phenyl radicals, (iii) a phenolicmaterial having the structural formula ##STR5## where R₁, R₂, X and Yare as hereinbefore identified. (iv) the product of reacting (a) adialkylated phenol having the structure ##STR6## where R₁₁ R₁₂ and R₁₃are selected from hydrogen and saturated alkyl radicals having 1 to 8carbon atoms, where R₁₁ and R₁₃ radicals are preferably selected fromhydrogen and saturated alkyl radicals having 4 to 6 carbon atoms, with(b) an unsaturated hydrocarbon, preferably a diolefin having 5 to 10carbon atoms, such as piperylene, isoprene, cyclooctadiene,dicyclopentadiene and allylbromide, (v) an amine compound having thestructure ##STR7## where R₁₄ is selected from hydrogen, methyl, ethyland methoxy radicals, where X₂ is selected from the groups consisting of--NH, --N--CH(CH₃)--CH₂ --CH₂ --CH₃, and oxygen and where Y₂ is selectedfrom the group consisting of --COCH=CH₂, ##STR8## and (vi) compoundsselected from N-(4-N-morphilinophenyl) acrylamide,N-acrylyl-2,2,4-trimethyl-1,2-dehydroquinoline andN-(4-anilinophenyl)maleimide.

In the practice of this invention, the said alkyl radicals for therequired phenol or amine compounds, such as those containing 1 to 8carbon atoms, 1 to 4 carbon atoms and 4 to 6 carbon atoms can be easilyselected from methyl, ethyl, isopropyl, isobutyl, t-butyl, isopentyl,t-pentyl, isohexyl, t-hexyl, isoheptyl, t-heptyl, isooctyl, t-octyl aswell as the normal hydrocarbon configurations of such radicals.

In further accordance with this invention, the age resistant resin isprepared by reacting, preferably in the presence of a diluent, at atemperature in the range of about 0° C to about 100° C, preferably about20° C to about 70° C, in the presence of a catalyst selected fromaluminum chloride, ethyl aluminum dichloride, boron trifluoride andboron trifluoride etherate, a mixture selected from:

A. about 40 to about 70 weight percent of said aliphatic diolefinshaving 4 to 8, preferably 4 to 6, carbon atoms, about 60 to about 20weight percent said aliphatic monoolefins having 3 to 8, preferably 4 to6, carbon atoms, about 0 to about 35 weight percent of at least one ofsaid dicyclopentadiene and vinyl aromatic compound and about 0.2 toabout 2 weight percent of at least one of said phenol and/or amine typecompounds and

B. about 0 to about 40 weight percent of said diolefins, about 10 toabout 40 weight percent of said monoolefins, about 40 to about 70 weightpercent of said vinyl aromatic compound and about 0.2 to about 2 weightpercent of at least one of said phenol and/or amine compounds.

In the preparation of the age resistant resin of this invention, variousaliphatic diolefins can be used, representative and preferable of whichare isoprene, 1,3-butadiene, piperylene and 2,3-dimethyl-1,3-butadiene.Further, various monoolefins can be used, particularly branched chainmonoolefins, representative of which are isobutylene, 2-methyl-1-butene,2-methyl-2-butene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene,2-methyl-1-pentene and 2-methyl-2-pentene. Generally, the isobutylene,2-methyl-1-butene and 2-methyl-2-butene are the preferred monoolefins.

Particularly advantageous age resistant resins can be prepared having asoftening point in the range of 80° C to about 110° C which compriseabout 40 to about 80 weight percent units derived from piperylene, about60 to about 20 weight percent units derived from monoolefins selectedfrom 2-methyl-1-butene and 2-methyl-2-butene and about 0.2 to about 2weight percent units derived from at least one of said selected phenoland/or amine type compounds, when such materials are polymerized in thepresence of aluminum chloride.

A further advantageous age resistant resin is prepared by polymerizingsuch materials in the presence of boron trifluoride or boron trifluorideetherate to produce a resin having a softening point in the range ofabout 0° C to about 30° C.

An additional advantageous age resistant resins having a softening pointin the range of about 70° C to about 110° C is prepared by polymerizinga mixture of such materials after addition of up to about 20 weightpercent of at least one vinyl aromatic compound selected from styreneand α-methyl styrene in the presence of aluminum chloride.

A further advantageous age resistant resin is prepared by polymerizingthe diolefin/monoolefins mixture to which has been added up to about 20weight percent dicyclopentadiene in the presence of aluminum chloride toresult in a composition having a softening point in the range of about80° C to about 140° C.

A further advantageous age resistant resin comprises about 10 to about40 weight percent of said diolefins, about 10 to about 40 weight percentof said monoolefins, about 40 to about 70 weight percent of at least oneof said vinyl aromatic compounds and about 0.2 to about 2 weight percentof at least one of said selected phenol or amine compounds when thematerials are polymerized in the presence of aluminum chloride orethylaluminum dichloride.

Another advantageous age resistant resin comprises about 10 to about 40weight percent of said monoolefins, particularly isobutylene, about 40to about 70 weight percent of at least one of styrene and α-methylstyrene, preferably a mixture of both styrene and α-methyl styrene andabout 0.2 to about 2 weight percent of at least one of said phenol andamine compounds in the presence of aluminum chloride or ethylaluminumdichloride.

In the practice of this invention, the materials are simply reacted inthe presence of a diluent and in the presence of the desired catalyst.Generally, where a higher softening point resin is desired the materialsare polymerized with aluminum chloride. Likewise, when a substantiallylower softening point resin is desired, the materials are polymerized inthe presence of boron trifluoride or boron trifluoride etherate. Variousdiluents can be used for the polymerization such as aromatichydrocarbons, alicyclic hydrocarbons and aliphatic hydrocarbons as wellas the unreacted monomers themselves. Representative examples of sucharomatic hydrocarbons are benzene, toluene and xylene. Representativeexamples of the various aliphatic hydrocarbons are pentane, hexane andheptane, and representative of the various alicyclic hydrocarbons arecyclohexane and cycloheptane. The polymerization can conveniently beconducted in batch form although a continuous system can be used ifdesired. The polymerization can be conducted at atmospheric pressure orabove or below atmospheric pressure. Generally a satisfactory pressureis the autogenous pressure developed by the system itself. The amount ofcatalyst used is not generally critical, although it is required that acatalytic amount be present in order to facilitate the polymerizationreaction.

The aluminum chloride is generally desired to be in particulate form inorder to enhance the rate of the reaction and to facilitate the use ofless catalyst. Generally the aluminum chloride particulate size is inthe range of about 5 to about 200 mesh, based on the U.S. standard meshsize, although larger or small sizes can be used.

The boron trifluoride or its etherate catalyst used for preparing theinitial hydrocarbon resin can be added before or after addition of themonomers. If boron trifluoride is used, it is generally charged to thesolution as a gas beneath the liquid surface in order to provide bettergas/liquid contact.

The boron trifluoride etherate catalyst is a complex of the type derivedfrom boron trifluoride and an ether having from 2 to 12, and preferablyfrom 2 to about 6, carbon atoms. The complex is generally represented bythe formula:

    BF.sub.3.sup.. OR.sub.2

representative of various ethers for preparation of the etherate arethose having the structure ROR', where R and R' are individuallyselected from saturated alkyl radicals having from 1 to about 6, andpreferably about 1 to about 3, carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, t-butyl, n-pentyl,isopentyl, t-pentyl, isohexyl, n-hexyl and t-hexyl radicals. The ethylradical is usually preferred. The complex, when not availablecommercially, can generally be prepared by reacting boron trifluoridegas with an ether in about equimolar quantities in an inert atmosphereat a temperature in the range of about -25° C to about 25° C, andusually in the range of about 10° C to about 25° C. Representative ofvarious ethers are dimethyl ether, diethyl ether, methyl ethyl ether,di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutylether, di-t-butyl ether, di-n-amyl ether, diisoamyl ether, di-t-amylether, ethyl amyl ether, diisohexyl ether, di-n-hexyl ether, di-t-hexylether and butyl (2-ethyl hexyl) ether. Diethyl ether is usuallypreferred.

The phenol and amine type compounds are necessary building blocks in thepractice of this invention in order to prepare the advantageousoxidative age resistant resin materials.

Representative of various phenol materials of structure (I) are

3,5-di-t-butyl-4-hydroxycinnamonitrile

ethyl-3,5-di-t-butyl-4-hydroxycinnamate

3,5-di-t-butyl-4-hydroxystyryl methyl ketone

3,5-di-t-butyl-4-hydroxycinnamamide

3,5-di-t-butyl-4-hydroxycinnamic acid

3,5-di-t-hexyl-4-hydroxycinnamonitrile

ethyl-3,5-di-t-hexyl-4-hydroxycinnamate

3,5-di-α-phenethyl-4-hydroxycinnamonitrile

ethyl-3,5-di-α-phenethyl-4-hydroxycinnamate

3-t-butyl-4-hydroxy-5-methyl-cinnamonitrile

ethyl-3-t-butyl-4-hydroxy-5-methylcinnamate

ethyl-3,5-diisopropyl-4-hydroxycinnamate

ethyl-3,5-dimethyl-4-hydroxycinnamate

ethyl-4-hydroxycinnamate

diethyl-3,5-di-t-butyl-4-hydroxybenzylidene malonate

3,5-di-t-butyl-4-hydroxybenzylidenemalonitrile

ethyl-3,5-di-t-butyl-4-hydroxybenzylidenecyanoacetate

3,5-di-t-butyl-4-hydroxybenzylidenecyanoacetamide

3-(3,5-di-t-butyl-4-hydroxybenzylidene)-2,4-pentanedione

diethyl-3,5-di-t-hexyl-4-hydroxybenzylidenemalonate

ethyl-3,5-di-t-hexyl-4-hydroxybenzylidenecyanoacetate and

ethyl-3,5-di-t-butyl-4-hydroxycinnamate.

Representative examples of various phenolic compounds having thestructure (II) are:

3,5-di-t-butyl-4-hydroxyphenylacrylate

3,5-di-t-butyl-4-hydroxyphenylmethacrylate

3,5-di-t-butyl-4-hydroxyphenylcrotonate

3,5-di-t-butyl-4-hydroxyphenylcinnamate

3,5-di-t-butyl-4-hydroxybenzylacrylate

3,5-di-t-butyl-4-hydroxybenzylmethacrylate

3,5-di-t-butyl-4-hydroxybenzylcrotonate

3,5-di-t-butyl-4-hydroxybenzylcinnamate

N-(3,5-di-t-butyl-4-hydroxyphenyl)acrylamide

N-(3,5-di-t-butyl-4-hydroxyphenyl)methacrylamide

N-(3,5-di-t-butyl-4-hydroxyphenyl)crotonamide

N-(3,5-di-t-butyl-4-hydroxyphenyl)cinnamamide

N-(3,5-di-t-butyl-4-hydroxybenzyl)acrylamide

N-(3,5-di-t-butyl-4-hydroxybenzyl)methacrylamide

N-(3,5-di-t-butyl-4-hydroxybenzyl)crotonamide

N-(3,5-di-t-butyl-4-hydroxybenzyl)cinnamamide

2-(3,5-di-t-butyl-4-hydroxybenzyloxy)ethyl acrylate

2-(3,5-di-t-butyl-4-hydroxybenzyloxy)ethyl methacrylate

2-(3,5-di-t-butyl-4-hydroxybenzyloxy)ethyl crotonate and

2-(3,5-di-t-butyl-4-hydroxybenzyloxy)ethyl cinnamate

A representative example of a compound having structure (III) is2-hydroxy-2-t-butyl-5-methylstyryl methyl ketone.

Representative examples of various amine compounds having the structure(IV) are:

N-(4-anilino phenyl) acrylamide

N-(4-anilino phenyl) methacrylamide

N-(4-anilino phenyl) crotonamide

N-(4-anilino phenyl) cinnamamide

N-(4-toluidino phenyl) acrylamide

N-(4-toluidino phenyl) methacrylamide

N-(4-toluidino phenyl) crotonamide

N-(4-toluidino phenyl) cinnamamide

N-[4-(p-methoxy)anilinophenyl]acrylamide

N-[4-(p-methoxy)anilinophenyl]methacrylamide

N-[4-(p-methoxy)anilinophenyl]crotonamide

N-[4-(p-methoxy)anilinophenyl]cinnamamide

4-anilinophenyl acrylate

4-anilinophenyl methacrylate

4-anilinophenyl crotonate

4-anilinophenyl cinnamate

N-(4-anilinoanilinomethyl) maleimide

N-(4-anilinoanilinomethyl) acrylamide and

N-(4-anilinophenyl)maleamic acid

The oxidative age resistant resins of this invention can uniquely beused as tackifiers for natural rubber and synthetic rubber, includingpressure sensitive adhesives, as well as for thermoplastic polymers usedin hot melt adhesives. Particularly advantageous are thepiperylene/2-methyl-2-butene back-boned resins and theisobutylene-styrene/α-methyl styrene with and without isobutyleneformulated resins.

For example, the oxidative age resistant resins can impart building tackas well as inherent age resistance with enhanced resistance to migrativedilution when an admixture is formed thereof.

Therefore, in accordance with this invention, a rubbery compositionhaving enhanced resistance to oxidative aging comprises 100 parts byweight of a rubber selected from natural rubber and synthetic rubber inadmixture with about 1 to about 10 parts by weight of the age resistantresin of this invention.

The oxidative age resistant resin has further valuable utility for thepreparation of pressure sensitive adhesives.

Therefore, in further accordance with this invention, a pressuresensitive adhesive is provided which comprises 100 parts by weight of arubber selected from natural rubber and synthetic rubber in admixturewith about 40 to about 250 parts by weight of the age resistant resin ofthis invention.

Representative examples of various synthetic rubbers to which the ageresistant resin can be admixed are rubbery polymers of conjugated dienesincluding polybutadiene and polyisoprene, copolymers and blockcopolymers of such dienes with styrene such as rubbery butadiene/styreneand butadiene/acrylonitrile copolymers, butyl rubber as a polymerizationproduct as a major portion of isobutylene and a minor portion of adiolefin such as 1,3-butadiene or isoprene, copolymers of ethylene andpropylene, terpolymers of ethylene, propylene and a minor portion of aconjugated diene. It is to be understood that mixtures of such rubberstocks including reclaimed rubber can be used. The said block areparticularly preferred for pressure sensitive adhesives.

The oxidative age resistant resins of this invention have furtherutility for use as tackifiers in hot melt adhesives. Indeed, theirutility is enhanced by practically locking the antioxidants into the hotmelt adhesives thereby substantially inhibiting the ability of theantioxidant to migrate from the system, even when it is required toremain in its heated molten condition over a period of time.

Therefore, in accordance with this invention, a hot melt adhesive systemcomprises 100 parts of a thermoplastic material selected frompolyethylene having a molecular weight of about 1500 to about 21000,isotactic and atactic polypropylene, ethylene/ethylacrylate copolymersand ethylene/vinyl acetate copolymers in admixture with about 10 toabout 70 parts by weight of the oxidative age resistant resin of thisinvention.

The practice of this invention is further illustrated by reference tothe following example which is intended to be representative rather thanrestrictive of the scope of the invention. Unless otherwise indicated,all parts and percentages are by weight.

EXAMPLE I

A series of resins having a built-in antioxidant were prepared accordingto the following method.

To a series of reactors, indentified herein as Experiments A-H, wascharged 3 parts particulate aluminum chloride and 50 to 100 partsheptane. To a hydrocarbon mixture comprising primarily piperylene and2-methyl-2-butene was added 0.25 to 0.75 part of various phenolic andamine compounds. The hydrocarbon mixtures were then charged to theindividual reactors containing the aluminum chloride and heptane over aperiod of 1.5 hours with the reaction temperature maintained around25°-30° C. The polymerization reaction was allowed to proceed, afteraddition of all of the materials, for about 1 hour at the maintainedtemperature of about 25° to about 30° C. The polymerization reaction wasterminated by the addition of 10 parts methanol and 15-20 parts lime.The resulting polymerizate solution was filtered and the filtrate steamdistilled using 250° C steam at essentially atmospheric pressure. Thesteam distillation was continued until about 2 parts of water had beencollected for 1 part of resin.

The resulting resins exhibited yields in the range of about 45 to about55 percent, softening points in the range of about 88° C to about 101°C, and Gardner colors in the range of about 3 to about 6.

The resins were then tested for their utility as anantioxidant-containing resin by measuring the time required for thesample to absorb 1 percent oxygen. [Test method reference -- Shelton, J.R. and Winn, H., Industrial & Engineering Chemistry 38,71 (1946)]

The following Table 1 more clearly shows the resin preparationparameters and the results of the antioxidant test. Experiment A was acontrol to which no antioxidant had been added to the monomer mixture.

                  TABLE 1                                                         ______________________________________                                                           %         S.P.   Hours to                                  Exp  Antioxidant   Antioxidant                                                                             (° C)                                                                         1% oxygen                                 ______________________________________                                        A    none          0         96     18.0                                      B    N-(4-anilino                                                                  phenyl)-methacryl                                                             amide         0.5       92     41.9                                      C    N-(1,3-dimethyl-                                                              butyl)-N-(p-anilino                                                           phenyl)acrylamide                                                                           0.5       88     55.7                                      D    3,5-di-t-butyl-4-                                                                           0.25      100.5  93.8                                           hydroxy-phenyl                                                                methacrylate                                                             E    "             0.5       97.5   257.8                                     F    "             0.75      96.0   279.6                                     G    Ethyl-3,5-di-t-                                                               butyl-4-hydroxy-                                                              cinnamate     0.5       101    158.3                                     H    Diethyl-3,5-di-                                                               t-butyl-4-hydroxy-                                                            benzylidine-  0.5       100    172.8                                          malonate                                                                 ______________________________________                                    

Thus, this example demonstrates that the resins of this inventionexhibit a substantially improved built-in antioxidant capability. They,therefore, have particularly valuable utility for use in admixture withvarious rubbers and thermoplastics which are to be exposed to oxidativedegradive conditions.

In this example, the hydrocarbon mixture used to prepare the ageresistant resin contained about an equal molar amount of piperylene and2-methyl-2-butene to which was added the various amounts of selectedphenolic and amine compounds.

While certain representative embodiments and details have been shown forthe purpose of illustrating the invention, it will be apparent to thosehaving skill in this art that various changes and modifications may bemade therein without departing from the spirit or scope of theinvention.

What is claimed is:
 1. An age resistant tackifying resin which comprisesa composition having a softening point in the range of 0° C. to about140° C. comprising (1) about 40 to about 80 weight percent units derivedfrom aliphatic diolefins selected from piperylene, 1,3-butadiene and2,3-dimethyl-1,3-butadiene, (2) about 60 to about 20 weight percentunits derived from aliphatic monoolefins selected from isobutylene,2-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-1-butene,2,3-dimethyl-2-butene, 2-methyl-1-pentene, and 2-methyl-2-pentene, wherethe mole ratio of diolefin to monoolefin is about 0.7/1 to about 2:1,(3) about 0 to about 40 weight percent units derived from at least oneof dicyclopentadiene and a vinyl aromatic compound selected from styreneand α-methyl styrene and (4) about 0.2 to about 2 weight percent unitsderived from at least one selected amine type compound, where said aminecompounds are selected from an amine compound having the structure##STR9##where R₁₄ is selected from hydrogen, methyl, ethyl and methoxyradicals, where X₂ is selected from the groups consisting of --NH,--N--CH(CH₃)--CH₂ --CH₂ --CH₃, and oxygen and where Y₂ is selected fromthe group consisting of --COCH=CH₂, ##STR10##
 2. The age resistantcomposition of claim 1 where said aliphatic diolefin is piperylene andwhere said monoolefin is primarily selected from 2-methyl-1-butene and2-methyl-2-butene.
 3. The age resistant composition of claim 1 having asoftening point in the range of about 80° C to about 110° C whichcomprises about 40 to about 80 weight percent units derived frompiperylene, about 60 to about 20 weight percent units derived frommonoolefins selected primarily from 2-methyl-1-butene and2-methyl-2-butene and about 0.2 to about 2 weight percent units derivedfrom at least one of said selected amine type compounds, when suchmaterials are polymerized in the presence of aluminum chloride.
 4. Theage resistant resin composition of claim 1 having a softening point inthe range of about 0° C to about 30° C which comprises about 40 to about80 weight percent units derived from piperylene, about 60 to about 20weight percent units derived from monoolefins selected from2-methyl-1-butene and 2-methyl-2-butene and about 0.2 to about 2 weightpercent units derived from at least one of said amine type compounds,when such materials are polymerized in the presence of boron trifluorideor boron trifluoride etherate.
 5. An age resistant resin compositionaccording to claim 3 having a softening point in the range of about 70°C to about 110° C prepared by polymerizing said materials after theaddition of up to about 20 weight percent of at least one vinyl aromaticcompound selected from styrene and α-methyl styrene.
 6. The ageresistant resin of claim 1 where said amine compounds are selectedfromN-(4-anilino phenyl)acrylamide N-(4-anilino phenyl)methacrylamideN-(4-anilino phenyl)crotonamide N-(4-anilino phenyl)cinnamamideN-(4-toluidino phenyl)acrylamide N-(4-toluidino phenyl)methacrylamideN-(4-toluidino phenyl)crotonamide N-(4-toluidino phenyl)cinnamamideN-[4-(p-methoxy)anilinophenyl]acrylamideN-[4-(p-methoxy)anilinophenyl]methacrylamideN-[4-(p-methoxy)anilinophenyl]crotonamideN-[4-(p-methoxy)anilinophenyl]cinnamamide 4-anilinophenyl acrylate4-anilinophenyl methacrylate 4-anilinophenyl crotonate 4-anilinophenylcinnamate N-(4-anilinoanilinomethyl)maleimideN-(4-anilinoanilinomethyl)acrylamide and N-(4-anilinophenyl)maleamicacid.